Polymers with urea groups and silyl groups and production and use thereof

ABSTRACT

A process for the production of compounds which contain at least one urea group and at least one silyl group. The process involves reacting a compound containing at least one amino group and a carbamate compound. The compounds produced by this process are useful as surface coating compositions, foams and adhesives.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a national stage application under 35 USC 371 ofinternational application PCT/EP01/12291 filed on Oct. 24, 2001, theinternational application not being published in English. Thisapplication also claims priority under 35 USC 119 to DE 100 53 545.3,filed on Oct. 27, 2000.

BACKGROUND OF THE INVENTION

This invention relates to a process for the production of compoundscontaining at least one urea group and at least one silyl group, inwhich a compound containing at least one amino group is reacted with acarbamate, either the compound with at least one amino group or thecarbamate bearing a silyl group, to compounds produced by this process,to their use and to surface coating compositions, foams and adhesivescontaining these compounds.

Organic compounds, especially polymers, which contain both a silyl groupand a urea group are used in many branches of industry, for example inthe coating or adhesives field. The advantages of such compounds,especially the polymers, lie in particular in their ability both tohydrophobicize and to impart a binding effect to hydrophilic substratesand also to crosslink with one another under the effect of moisture.

Surface coating compositions containing the above-mentioned compoundsshow improved adhesion both on hydrophobic and on hydrophilic surfaces.Adhesives containing such polymers are capable, for example, ofpermanently bonding both hydrophilic and hydrophobic substrates andsubstrates of different polarity to one another.

Hitherto, the simultaneous introduction of urea groups and silyl groupsinto polymers has been difficult for a variety of reasons. In manycases, isocyanatosilanes have been used to introduce such groups eventhough they were unpopular among manufacturers of such products becauseof their toxicity and their sensitivity to water. In addition, residuesof isocyanatosilanes often could not be removed to a satisfactory levelfrom the compounds thus produced so that a residual content ofisocyanates often resulted in an obligation to declare the compoundsthemselves or products produced from them. However, the declaration ofsuch ingredients reduces consumer acceptance of the products producedfrom them.

However, the problem illustrated here with reference by way of exampleto the interplay between urea groups and silyl groups also applies inprinciple to many other methods of introducing structural elementsobtainable using isocyanate groups into polymers. The presence ofisocyanates in reaction mixtures often leads to the formation ofunwanted products or to isocyanate-containing material remaining in theend product so that the problems mentioned above arise.

A process for the production of polyethers containing both a urea groupand an alkoxysilyl group is described, for example, in ChemicalAbstracts 123:171406 (abstract of JP 93-185 595). To produce thesecompounds, an aminofunctional polyether is reacted with a silyl compoundcontaining as isocyanate group.

U.S. Pat. No. 5,886,205 relates to a process for the production ofisocyanate compounds containing silyl groups which comprises the thermaldecomposition of carbamic acid esters containing silyl groups in thepresence of a catalyst. The reaction of a carbamate with a compoundcontaining at least one amino group is not mentioned in this document.

U.S. Pat. No. 5,218,133 relates to a process for the production of silylcarbamates or silyl isocyanurates, in which an aminosilane is reactedwith a dialkyl carbonate, diaryl carbonates or a mixture thereof in thepresence of a basic catalyst to give a silyl organocarbamate. The basiccatalyst is then optionally neutralized and residual aminosilane isneutralized. After addition of a decomposition catalyst and heatingunder reduced pressure, a silyl isocyanurate is obtained. However, thecited document does not describe how silyl compounds containing ureastructural elements can be obtained by reaction of carbamates with aminocompounds, either the amino compound or the carbamate or both containinga silyl group.

U.S. Pat. No. 6,008,396 describes a process for the production of anisocyanato-organsosilane, in which a carbamato-organosilane is convertedinto an isocyanato-organosilane in an inert liquid medium. Theproduction of compounds containing both a urea group and a silyl groupis not mentioned in the cited document.

U.S. Pat. No. 5,886,205 describes a process for the production of anisocyanate containing silyl groups in which a carbamic acid estercontaining silyl groups is decomposed in the presence of a catalyst at apH value of at most 8. A process for the production of compoundscontaining both urea groups and silyl groups is not described in thecited document.

In addition, many combinations of structural elements obtainable usingisocyanate groups and silyl groups have hitherto only been obtainable bymultistage and hence expensive processes. This applies in particular tothe production of polymers containing both isocyanurate groups and ureaand silyl groups. Such polymers are of considerable interest with regardin particular to their crosslinking and hence to the resulting materialproperties of surface coating compositions and adhesives.

EP-A 1 006 132 relates to alkoxysilane-containing lacquer preparationsproduced using 4,4′-diisocyanatodicyclohexyl methane polyisocyanates.The cited document describes, for example, the reaction ofpolyisocyanates obtainable by trimerization of4,4′-diisocyanatodicyclohexyl methane with aminofunctionalalkoxysilanes. Unfortunately, the described reaction has thedisadvantage that isocyanurates generally containing low molecularweight diisocyanates are used. Low molecular weight isocyanates such asthese have a considerable toxic potential. In addition, the crosslinkingof a polymer produced using such isocyanurates is difficult to controlbecause the isocyanurates described in the cited document alwaysrepresent a complex mixture of compounds differing in theirfunctionality in which isocyanurates having a functionality of more thanthree are always present. The use of such mixtures involves thedisadvantage for the user that the properties of a polymer producedusing these triisocyanatotriisocyanurate mixtures are difficult toadjust in view of slight crosslinking. Another disadvantage of thecompounds described in the cited document is that a urea group or aurethane group is always present in the immediate vicinity of theisocyanurate group because of the structure of the isocyanurates used.This constellation complicates or prevents the production of highlyflexible binders because this direct proximity of the functional groupsmentioned generally leads to hard brittle binders.

In addition, the presence of urethane groups reduces the thermalstability of these compounds because urethane groups split at ca.140–160° C. Unfortunately, such behavior prevents the use of suchcompounds in heat-resistant applications.

Another disadvantage of the described compounds is that isocyanuratescontaining isocyanate groups are difficult to produce. On account of thedanger of crosslinking, which increases with increasing conversion, thetrimerization of isocyanates to isocyanurates can only be carried out toa certain degree below a corresponding crosslinking point. Theisocyanate originally used for crosslinking and the isocyanuratecontaining isocyanate groups obtained as product then have to beseparated in complicated distillation processes. After distillation, theisocyanate distilled off is returned to the trimerization process. Thevolume/time yields of such a process are poor on account of the complexseparation steps.

SUMMARY OF THE INVENTION

Accordingly, there was a need for a process that would lead to polymerscontaining both at least one urea group and a silyl group in which thedisadvantages mentioned above would be avoided. In addition, there was aneed for polymers containing isocyanurate groups, urea groups and silylgroups which would not attended by any of the disadvantages mentionedabove.

The problem addressed by the present invention is solved by a processfor the production of compounds containing at least one urea group andat least one silyl group, by compounds produced by this process, bypolymers containing at least one isocyanurate group and at least onesilyl group, by processes for the production of such polymers and by theuse of the compounds produced by the process according to the inventionand the compounds according to the invention in surface coatingcompositions, foams or adhesives.

DETAILED DESCRIPTION OF THE INVENTION

Accordingly, the present invention relates firstly to a process for theproduction of compounds containing at least one urea group and at leastone silyl group, in which a compound containing at least one amino groupand a carbamate are reacted as reactants, at least one of the reactantscarrying a silyl group.

A “urea group” in the context of the present invention is understood tobe a structural element corresponding to general formula I:

in which R⁸ is hydrogen and R⁹ is hydrogen, a linear or branched alkylgroup containing 1 to 24 carbon atoms, an optionally substituted arylgroup containing 6 to 24 carbon atoms, an alkyl or arylsilyl group. Thesubstituent R⁹ may also contain one or more substituents, such as estergroups, keto groups, amino groups or hydroxyl groups. The substituent R⁹is preferably hydrogen or a linear or branched alkyl group containing 1to 12 carbon atoms, more particularly hydrogen.

A “silyl group” in the context of the present invention is understood tobe a compound corresponding to general formula II:

in which R¹ to R⁶ independently of one another represent a linear orbranched, saturated or unsaturated hydrocarbon radical containing 1 toabout 24 carbon atoms, a saturated or unsaturated cycloalkyl groupcontaining 4 to about 24 carbon atoms or an aryl group containing 6 toabout 24 carbon atoms, n, m and j are each integers of 0 to 3 (m+n+j=3),a is an integer of 0 to 3, b is an integer of 0 to 2 and c is a numberof 0 to 8.

In a first embodiment of the present invention, a compound containing asilyl group corresponding to general formula II is used as at least onereactant. Suitable compounds are in particular compounds correspondingto general formula III:

in which R¹ to R⁶, a, b, c, n, m and j are as defined above, R⁷ is anoptionally substituted alkylene group containing 1 to about 44 carbonatoms, an optionally substituted cycloalkylene group containing 6 toabout 24 carbon atoms or an optionally substituted arylene groupcontaining 6 to about 24 carbon atoms and Z is an amino group or acarbamate group. Suitable substituents are, for example, functionalgroups, such as thioether, mercapto, amino, ester, amido, nitro or ethergroups or mixtures of two or more thereof.

A “carbamate group” in the context of the present invention isunderstood to be a structural element corresponding to general formulaIV:

in which the substituent R¹⁰ is a linear or branched, saturated orunsaturated alkyl group containing 1 to about 10 carbon atoms, asaturated or unsaturated cycloalkyl group containing about 6 to about 24carbon atoms or an aryl group containing 6 to about 24 carbon atoms.

In a preferred embodiment of the present invention, compoundscorresponding to general formula II, in which Z is an amino group, areused as at least one reactant. Compounds such as these are also referredin the present specification as aminosilanes.

Suitable aminosilanes are, for example,N-(α-methyldimethoxysilylmethyl)-amine,N-α-trimethoxysilylmethyl)-amine, N-α-diethylmethoxy-silylmethyl)-amine,N-(α-ethyldimethoxysilylmethyl)-amine,N-α-methyldiethoxysilylmethyl)-amine, N-(α-triethoxysilylmethyl)-amine,N-α-ethyldiethoxysilylmethyl)-amine,N-(β-methyldimethoxysilylethyl)-amine, N-(β-trimethoxysilylethyl)-amine,N-(β-ethyldimethoxysilylethyl)-amine,N-(β-methyldiethoxysilylethyl)-amine, N-(β-triethoxysilylethyl)-amine,N-(β-ethyldiethoxysilylethyl)-amine,N-(γ-methyldimethoxysilylpropyl)-amine,N-(γ-trimethoxysilylpropyl)-amine,N-(γ-ethyldimethoxysilylpropyl)-amine,N-(γ-methyldiethoxysilylpropyl)-amine, N-(γ-triethoxysilylpropyl)-amine,N-(γ-ethyldiethoxysilylpropyl)-amine,N-(4-methyldimethoxysilylbutyl)-amine, N-(4-trimethoxysilylbutyl)-amine,N-(4-triethylsilylbutyl)-amine, N-(4-diethylmethoxysilylbutyl)-amine,N-(4-ethyldimethoxysilylbutyl)-amine,N-(4-methyldiethoxysilylbutyl)-amine, N-(4-triethoxysilylbutyl)-amine,N-(4-diethylethoxysilylbutyl)-amine,N-(4-ethyldiethoxysilylbutyl)-amine,N-(5-methyldimethoxysilylpentyl)-amine,N-(5-trimethoxysilylpentyl)-amine, N-(5-triethylsilylpentyl)-amine,N-(5-ethyldimethoxysilylpentyl)-amine,N-(5-methyldiethoxysilylpentyl)-amine, N-(5-triethoxysilylpentyl)-amine,N-(5-diethylethoxysilylpentyl)-amine,N-(5-ethyldiethoxysilylpentyl)-amine,N-(6-methyldimethoxysilylhexyl)-amine, N-(6-trimethoxysilylhexyl)-amine,N-(6-ethyldimethoxysilylhexyl)-amine,N-(6-methyldiethoxysilylhexyl)-amine, N-(6-triethoxysilylhexyl)-amine,N-(6-ethyldiethoxysilylhexyl)-amine,N-[γ-tris-(trimethoxysiloxy)silylpropyl]-amine,N-[γ-tris(trimethoxysiloxy)silylpropyl]-amine,N-(γ-trimethoxysiloxydimethylsilylpropyl)-amine,N-(γ-trimethyl-siloxydimethoxysilylpropyl)-amine,N-(γ-triethoxysiloxydiethylpropyl)-amine,N-(γ-triethoxysiloxydiethoxysilylpropyl)-amine,N,N-butyl-(γ-trimethoxy-silylpropyl)-amine,N,N-butyl-(γ-triethoxysilylpropyl)-amine,N,N-phenyl-(γ-trimethoxysilylpropyl)-amine,N,N-phenyl-(γ-triethoxysilylpropyl)-amine,N,N-cyclohexyl-(γ-trimethoxysilyipropyl)-amine,N,N-ethyl-(γ-trimethoxysilyl-propyl)-amine,diethyl-N-(trimethoxysilylpropyl)-aspartate,diethyl-N-(triethoxysilylpropyl)-aspartateN,N-ethyl-(γ-dimethoxymethylsilylpropyl)-amine,N,N-ethyl-(γ-trimethoxysilylisobutyl)-amine,N,N-Bis-(trimethoxy-propyl)-amine,N,N-ethyl-(γ-trimethoxysilylisobutyl)-amine,N,N-ethyl-(α-trimethoxysilylmethyl)-amine,dibutyl-N-(trimethoxysilylpropyl)-aspartate,dibutyl-N-(triethoxysilylpropyl)-aspartat,N,N-(β-aminopropyl)-(γ-trimethoxy-silylpropyl)-amine,N,N′-di-(trimethoxysilylpropyl)-ethylenediamine,tetra-(trimethoxysilylpropyl)-ethylendiamine andN,N-ethyl-(β-trimethoxysilyl-ethyl)-amine orN-[γ-tris(trimethylsiloxy)silylpropyl]-amine or mixtures of two or morethereof.

In addition, aminosilanes corresponding to general formula III in whichthe recurring unit characterized by the parameter c is a recurring unitcorresponding to general formula V:

where c has a value of 1 to about 6, may also be used in accordance withthe invention.

Carbamatosilanes corresponding to general formula III in which Z is acarbamate group corresponding to general formula IV are also suitablefor use as reactants in accordance with the invention.

Carbamatosilanes corresponding to general formula III can be obtained,for example, by reaction of an aminosilane with a dialkyl or diarylcarbonate or pyrocarbonate or a mixture of two or more thereof. Such areaction is normally carried out in the presence of a basic catalyst.Basically, however, any other known processes for the production ofcarbamates may also be used providing they are suitable for theproduction of carbamatosilanes, for example the reaction of aminosilaneswith chloroformic acid esters or the reaction of isocyanatosilanes withalcohols.

Suitable carbonates are, for example, dimethyl carbonate, diethylcarbonate, dipropyl carbonate, dibutyl carbonate, diisobutyl carbonate,di-tert.butyl carbonate, diisopentyl carbonate, diisopropyl carbonate,ethylmethyl carbonate, ethyl-2-butoxyethyl carbonate,bis-(2-chloroethyl)-carbonate, diphenyl carbonate,bis-(o,m-chlorophenyl)-carbonate, bis-(o,p-chlorophenyl)-carbonate,bis-(dichlorophenyl)-carbonate, bis-(trichloro-phenyl)-carbonate orbis-(o-,m-,p-tolyl)-carbonate or mixtures of two or more thereof.

Carbamatosilanes produced using dimethyl carbonate, diethyl carbonate ordipropyl carbonate or pyrocarbonate or mixtures of two or more thereofare preferably used in accordance with the invention.

Suitable dialkyl pyrocarbonates are, for example, dimethylpyrocarbonate, diethyl pyrocarbonate or di-tert.butyl pyrocarbonate. Thereaction between the aminosilane and the organic carbonate may becarried out, for example, using stoichiometric quantities of thereactants. However, it is also possible, and often preferable, to use anexcess of organic carbonate of about 0.05 to about 1 mol per molaminosilane. Good results can be obtained, for example with a carbonateexcess of about 0.1 to about 0.4 mol per mol aminosilane. In the case ofrelatively high molecular weight silanes, for example with a molecularweight of more than about 200 or more than about 500, or in the case ofaminosilanes with a sterically hindered amino group, it may be necessaryto use an even larger excess of carbonate.

The reaction between aminosilane and carbonate is normally catalyzed bya basic catalyst. A strongly basic catalyst is preferably used. Suitablebasic catalysts are, for example, the alkali metal alkoxides obtainableby reaction of monohydric alcohols with alkali metals. Suitable alkalimetals are, for example, lithium, sodium or potassium; suitablemonohydric alcohols are, for example, methanol, ethanol, propanol orbutanol. Suitable strongly basic catalysts are, in particular, sodiummethanolate, sodium ethanolate, sodium propanolate, sodiumtert.butanolate, potassium methanolate, potassium ethanolate, potassiumpropanolate or potassium tert.butanolate and the like.

The quantity of catalyst during the reaction is about 0.01 to about 2%by weight, based on carbonate and aminosilane used.

The reaction between aminosilane and organic carbonate is slightlyexothermic. Normally, the aminosilane and organic carbonate are reactedwith one another in the presence of the basic catalyst in such a waythat the reaction temperature remains in the range from about 10 toabout 120° C., for example in the range from about 20 to about 80° C. orin the range from about 25 to about 60° C. The stability of thetemperature within these ranges may be achieved, for example, by typicalcooling processes, such as cold water, ice bath, dry ice bath or bycontrolling the rate at which the reactants are added. The reaction isnormally carried out at ambient pressure in an inert gas atmosphere.

On completion of the reaction, catalyst remaining in the reactionmixture and excess aminosilane are neutralized by addition of aneutralizing agent. Suitable neutralizing agents are, for example,inorganic acids, such as water-free hydrochloric acid, water-freephosphoric acid, or organic acids, such as glacial acetic acid,propionic acid, butyric acid, hexanoic acid, oleic acid, maleic acid,fumaric acid, succinic acid and the like. Weak organic acids, such asglacial acetic acid, or inorganic acids, such as water-free phosphoricacids, for example superphosphoric acid or polyphosphoric acid, or—wherethey exist—anhydrides thereof are preferably used for neutralization. Itis particularly suitable to use anhydrides of the corresponding acidsbecause both the catalyst and excess amine are bound. The reactionproduct may be separated off by typical known methods. The separation ofprecipitated salts by filtration, for example through silica gel or asuitable filter paper, and subsequent removal of volatile components byreduced pressure or an increase in temperature or both is particularlysuitable.

Particularly suitable carbamatosilanes corresponding to general formulaIII are, for example, methyl-N-α-methyldimethoxysilylmethyl)-carbamate,methyl-N-(α-trimethoxysilylmethyl)-carbamate,methyl-N-(α-ethyldimethoxysilylmethyl)-carbamate,methyl-N-(α-methyldiethoxysilyl-methyl)-carbamate,methyl-N-(α-triethoxysilylmethyl)-carbamate,methyl-N-(β-methyldimethoxysilylethyl)-carbamate,methyl-N-(β-trimethoxysilylethyl)-carbamate,methyl-N-(β-diethylmethoxysilylethyl)-carbamate,methyl-N-(β-ethyldimethoxysilylethyl)-carbamate,methyl-N-(β-methyldiethoxysilylethyl)-carbamate,methyl-N-(β-triethoxysilylethyl)-carbamate,methyl-N-(β-ethyldi-ethoxysilylethyl)-carbamate,methyl-N-(γ-methyldimethoxysilylpropyl)-carbamate,methyl-N-(γ-trimethoxysilylpropyl)-carbamate,methyl-N-(γ-ethyldimethoxysilylpropyl)-carbamate,methyl-N-(γ-methyldiethoxysilyl-propyl)-carbamate,methyl-N-(γ-triethoxysilylpropyl)-carbamate,methyl-N-(γ-ethyldiethoxysilylpropyl)-carbamate,methyl-N-(4-trimethoxysilylbutyl)-carbamate,methyl-N-(4-ethyldimethoxysilylbutyl)-carbamate,methyl-N-(4-methyldiethoxysilylbutyl)-carbamate,methyl-N-(4-triethoxysilylbutyl)-carbamate,methyl-N-(4-ethyldiethoxysilylbutyl)-carbamate,methyl-N-(5-methyldimethoxysilylpentyl)-carbamate,methyl-N-(5-trimethoxysilylpentyl)-carbamate,methyl-N-(5-ethyldimethoxysilylpentyl)-carbamate,methyl-N-(5-methyldiethoxysilylpentyl)-carbamate,methyl-N-(5-triethoxysilylpentyl)-carbamate,methyl-N-(5-ethyldiethoxysilylpentyl)-carbamate,methyl-N-(6-trimethoxysilylhexyl)-carbamate,methyl-N-(6-ethyldimethoxysilylhexyl)-carbamate,methyl-N-(6-triethoxysilylhexyl)-carbamate,methyl-N-(6-ethyl-diethoxysilylhexyl)-carbamate,methyl-N-[γ-tris-(trimethoxysiloxy)-silylpropyl]-carbamate,ethyl-N-(α-methyldimethoxysilylmethyl)-carbamate,ethyl-N-(α-trimethoxysilylmethyl)-carbamate,ethyl-N-(α-methyldiethoxysilylmethyl)-carbamate,ethyl-N-α-triethoxysilylmethyl)-carbamate,ethyl-N-α-ethyldiethoxysilylmethyl)-carbamate,ethyl-N-(β-methyldimethoxysilylethyl)-carbamate,ethyl-N-(β-trimethoxysilylethyl)-carbamate,ethyl-N-(β-ethyldimethoxysilylethyl)-carbamate,ethyl-N-(β-dimethylethoxysilylethyl)-carbamate,ethyl-N-(D-methyldiethoxysilylethyl)-carbamate,ethyl-N-(β-triethoxysilylethyl)-carbamate,ethyl-N-(γ-trimethoxysilylpropyl)-carbamate,ethyl-N-(γ-ethyldimethoxysilylpropyl)-carbamate,ethyl-N-(γ-methyldiethoxysilylpropyl)-carbamate,ethyl-N-(γ-triethoxysilylpropyl)-carbamate,ethyl-N-(γ-ethyldiethoxysilylpropyl)-carbamate,ethyl-N-(4-methyldimethoxysilylbutyl)-carbamate,ethyl-N-(4-trimethoxysilylbutyl)-carbamate,ethyl-N-(4-ethyldimethoxysilylbutyl)-carbamate,ethyl-N-(4-methyldiethoxysilylbutyl)-carbamate,ethyl-N-(4-triethoxysilylbutyl)-carbamate,ethyl-N-(4-ethyldiethoxysilylbutyl)-carbamate,ethyl-N-(5-methyldimethoxysilylpentyl)-carbamate,ethyl-N-(5-trimethoxysilylpentyl)-carbamate,ethyl-N-(5-ethyldimethoxysilylpentyl)-carbamate,ethyl-N-(5-triethoxysilylpentyl)-carbamate,ethyl-N-(5-ethyldiethoxysilylpentyl)-carbamate,ethyl-N-(6-methyldimethoxysilylhexyl)-carbamate,ethyl-N-(6-trimethoxysilylhexyl)-carbamate,ethyl-N-(6-ethyldimethoxysilylhexyl)-carbamate,ethyl-N-(6-methyldiethoxysilylhexyl)-carbamate,ethyl-N-(6-triethoxysilylhexyl)-carbamate,ethyl-N-[γ-tris-(trimethoxysiloxy)silylpropyl]-carbamate,methyl-N-[γ-tris(trimethoxysiloxy)silylpropyl]-carbamate,methyl-N-(γ-trimethoxysiloxydimethylsilylpropyl)-carbamate,methyl-N-(γ-trimethylsiloxydimethoxysilylpropyl)-carbamate,methyl-N-[γ-tris(triethoxysiloxy)silylpropyl]-carbamate,methyl-N-(γ-triethoxysiloxydiethylpropyl)-carbamate,methyl-N-(γ-triethoxysiloxydiethoxysilylpropyl)-carbamate,methyl-N-[γ-tris(trimethylsiloxy)silylpropyl]carbamate andmethyl-N-[6-tris(triethoxysiloxy)silylhexyl]-carbamate.Ethyl-N-[γ-tris(trimethoxysiloxy)silyl-propyl]-carbamate,ethyl-N-(γ-trimethoxysiloxydimethylsilylpropyl) carbamate,ethyl-N-(γ-trimethylsiloxydimethoxysilylpropyl)-carbamate,ethyl-N-[γ-tris(triethoxysiloxy)silylpropyl]-carbamate,ethyl-N-(γ-triethoxysiloxydiethylpropyl)-carbamate,ethyl-N-(γ-triethoxysiloxydiethoxysilylpropyl)-carbamate,ethyl-N-[γ-tris(trimethylsiloxy)silylpropyl]-carbamate andethyl-N-[6-tris-(triethoxysiloxy)silylhexyl]-carbamate.

In the process according to the invention, a compound containing atleast one amino group and a compound containing at least one carbamategroup, at least one of the compounds carrying a silyl group, are reactedwith one another. In the illustrated variants, i.e. where Z is an aminogroup or Z is a carbamate group, the above-mentioned compounds ofgeneral formula III satisfy the corresponding requirements. Accordingly,it is possible by the process according to the invention to producecompounds which contain one urea group and two silyl groups by reactingtwo compounds corresponding to general formula III with one another, oneof the compounds mentioned containing an amino group and one a carbamategroup. However, it is also possible in accordance with the invention forone of the reactants not to contain a silyl group.

Suitable reactants have, for example, a structure corresponding togeneral formula VI:R¹¹—(Z)_(p)  (VI)where Z is as already defined, p is a rational number of 1 to about1,000 and R¹¹ is a linear or branched, saturated or unsaturated,optionally substituted alkyl group containing 2 to about 44 carbonatoms, a saturated or unsaturated, optionally substituted cycloalkylgroup containing 6 to about 44 carbon atoms, an optionally substitutedaryl group containing 6 to about 44 carbon atoms, an isocyanurate ringor a polymer with a molecular weight of at least about 150.

In another embodiment of the present invention, a compound correspondingto general formula VI, in which Z is an amino group, is used as at leastone reactant in the process according to the invention. If, in acompound corresponding to general formula VI, Z is an amino group, atleast one other reactant corresponding to general formula III, in whichZ is a carbamate group, must be present in the reaction mixture.

If a compound corresponding to general formula VI, in which Z is anamino group, is used in the process according to the invention, thesubstituent R¹¹ may be, for example, a linear or branched, saturated orunsaturated, optionally substituted alkyl group containing 1 to about 44carbon atoms. Suitable alkyl groups have a length of, for example, 3 toabout 20 carbon atoms. If the alkyl group is unsubstituted, thecompounds corresponding to general formula VI are monoalkylamines.Suitable monoalkylamines are, for example, ethylamine, propylamine,butylamine, pentylamine, hexylamine and linear or branched higherhomologs thereof containing up to about 100 carbon atoms, the aminogroup being positioned either terminally or anywhere within the alkylgroup.

According to the invention, the substituent R¹¹ may also be asubstituted alkyl group. Suitable substituents are, for example,hydroxyl groups, ester groups, carboxylic acid groups, sulfonic acidgroups, phosphonic acid groups and the corresponding esters of the acidgroups mentioned.

In another embodiment of the present invention, the substituent R¹¹ hastwo or more groups Z, i.e. p is a number of 2 or more.

Accordingly, in another embodiment of the present invention, thereaction mixture may contain, for example, a compound VI with two ormore amino groups as a reactant. Suitable such compounds are, forexample, ethylenediamine, propylenediamine, butylenediamine,hexamethylenediamine, 2,4,4-trimethyl hexamethylenediamine,diethylenetriamine, 1,12-diaminododecane, diamines derived from dimerfatty acids or triamines derived from trimer fatty acids or a mixture oftwo or more of the compounds mentioned.

In another embodiment of the present invention, R¹¹ may be a saturatedor unsaturated, optionally substituted cycloalkyl group containing 6 toabout 24 carbon atoms. A corresponding cycloalkyl group may carry thesubstituents already mentioned above as substituents. In particular, thecycloalkyl group may contain one or more other amino groups. Suitablecycloalkyl compounds are, for example, cyclohexylamine,dicyclohexylamine, 1,4-cyclohexyldiamine,4,4′-dicyclohexylmethanediamine, isophoronediamine,1,3-bis-(aminomethyl)-cyclohexane, 1,4-bis(aminomethyl)-cyclohexane andhydrogenated toluenediamines, such as 1-methyl-2,4,-diaminocyclohexane,1-methyl-2,6-diaminocyclohexane and the like.

In another embodiment of the present invention, the compounds of generalformula VI used may be amines in which the substituent R¹¹ representsoptionally substituted aryl groups containing 6 to about 24 carbonatoms. Suitable substituents are in particular the substituents alreadymentioned in the foregoing. Particularly suitable aryl compoundscorresponding to general formula VI are, for example, aniline,1,4-diaminobenzene, aminotoluene, m- or p-phenylenediamine,diaminobiphenyl, p-methoxyaniline, p-chloroaniline, o-, m- orp-toluidine, 2,4-xylidine, 2,4- and 2,6-toluenediamine and correspondingmixtures, 4,4′-diphenylenediamine, methylene-bis-(anilines) including4,4′-methylenebis-(aniline), 2,4′-methylene-bis-(aniline),4,4′-oxy-bis-(aniline), 4,4′-carbonyl-bis-(aniline),4,4′-sulfonyl-bis-(aniline) or naphthyldiamines or mixtures of two ormore of the compounds mentioned.

In another embodiment of the present invention, the compounds of generalformula VI used may be amines in which the substituent R¹¹ representsoptionally substituted isocyanurates. Particularly suitable compoundsare 1,3,5-trisaminoalkyl, cycloalkyl and aryl isocyanurates. Thefollowing are mentioned as examples:1,3,5-tris-(6-aminohexyl)-isocyanurate,1,3,5-tris(6-aminopropy)-isocyanurate,1,3,5-tris(6-aminoethyl)-isocyanurate,1,3,5-tris-(3-aminophenyl)-isocyanurate and1,3,5-tris-(4-methyl-3-aminophenyl)-isocyanurate. Mixtures of two ormore of the compounds mentioned may also be used.

Another embodiment of the present invention is characterized by the useof compounds corresponding to general formula VI in which R¹¹ stands forone of the groups mentioned above which contains at least one carbamategroup as the functional group Z. Compounds such as these may be obtainedby reaction of the above-mentioned amino compounds with organiccarbonates or pyrocarbonates as already described in the presentspecification. Suitable compounds are, for example, compounds whichcontain only one carbamate group. However, compounds containing two ormore carbamate groups may also be used in the process according to theinvention. If a compound containing one or more carbamate groups is usedas the compound of general formula VI in accordance with the invention,at least one compound of general formula III where Z is an amino groupmust be used as a further reactant in the process according to theinvention.

In addition, compounds of general formula VI containing both an aminogroup and a carbamate group may also be used in accordance with theinvention. Such compounds may be obtained, for example, by reaction ofcompounds of the type described above containing more than one aminocompound with organic carbonates in a corresponding stoichiometricratio, for example in a molar ratio of 1:1 or less.

In another embodiment of the present invention, the substituent R¹¹ informula VI is a polymer.

In a preferred embodiment of the present invention, the polymer used isa polymer selected from the group consisting of polyacrylates,polymethacrylates, polystyrenes, polyesters, polyethers, polyamides,polyurethanes, polycarbonates, polylactones, polyethylenimine,polyureas, polyolefins and polyoxazolidones.

A “polymer” in the context of the present invention is understood to bea compound with a molecular weight of at least about 150 but preferablyhigher, for example at least about 500, 800 or at least about 1,000.

The polymers suitable for use as compounds of general formula VI inaccordance with the invention may contain, for example, only onefunctional group Z. However, it is equally possible, and preferred inaccordance with the invention, for the number of functional groups Z tobe more than 1, for example at least about 2, 3, 4, 5 or more.

According to the invention, the number p in general formula VI is arational number of 1 to about 1,000. The number p of functional groups Zin a polymer corresponding to general formula VI may then assume a valuediffering from an integer if the number of functional groups Z is takenas an average value in a mixture of molecules of general formula VI, thenumber of functional groups per molecule varying, as frequentlyencountered in polymer chemistry. Such variations can arise, forexample, due to the functionalization of a polymer in a polymer-analogreaction.

In a preferred embodiment of the present invention, the number p has avalue of about 1.5 to about 10, more particularly a value of about 1.8to about 5 and most particularly a value of about 1.9 to about 3.

In the context of the process according to the invention, a functionalgroup Z may be positioned terminally or laterally of the polymer chainR¹¹. If the number of functional groups Z is more than 1, two or morefunctional groups may be positioned both exclusively terminally and alsoexclusively laterally or terminally and laterally of a polymer chain.

According to the invention, suitable polymers R¹¹ are, for example,polymers obtainable by polymerization of compounds containing at leastone olefinically unsaturated double bond. Suitable polymers are, forexample, polyacrylates, polymethacrylates, polyvinyl esters, polyvinylethers, polyolefins or polystyrenes.

The molecular weight (M_(n)) of polymers suitable as R¹¹ is preferablyin the range from about 300 to about 1,000,000, more preferably in therange from about 500 to about 300,000 and most preferably in the rangefrom about 1,000 to about 30,000.

The molecular weight distribution of the polymers, which can bedetermined, for example, by gel permeation chromatography, based onpolystyrene as standard, under measuring conditions typically appliedfor polymers, need not be monomodal. A suitable polymer may also have abimodal or higher distribution.

The terms “polyacrylate” or “polyacrylates” used in the presentspecification apply in the following both to polymers or copolymers ofacrylic acid and/or derivatives thereof and to polymers or copolymers ofmethacrylic acid and/or derivatives thereof, unless otherwise indicatedin the text.

Polyacrylates can be produced by subjecting acrylic acid and/ormethacrylic acid and/or derivatives of acrylic acid and/or methacrylicacid, for example esters thereof with mono- or polyhydric alcohols,either individually or in the form of mixtures of two or more thereof,to polymerization in known manner, for example to radical, ionic ormetal-catalyzed polymerization.

According to the invention, both homo- and copolymers may be used aspolyacrylates. Besides the corresponding acrylates or methacrylates,suitable copolymers may also contain, for example, styrene,acrylonitrile, vinyl acetate, vinyl propionate, vinyl chloride,vinylidene chloride and/or butadiene.

Suitable monomers for the production of the polyacrylates are, inparticular, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutylacrylate, tert.butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate orlauryl acrylate and the corresponding esters of methacrylic acid.Acrylic acid, methacrylic acid, acrylamide or methacrylamide may also beadded in small quantities as further monomers during the polymerization.

Other acrylates and/or methacrylates containing one or more functionalgroups may optionally be present during the polymerization. These are,for example, maleic acid, itaconic acid, butanediol diacrylate,hexanediol diacrylate, triethylene glycol diacrylate, tetraethyleneglycol diacrylate, neopentyl glycol diacrylate, trimethylol propanetriacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate orpropylene glycol methacrylate.

The corresponding functional groups Z may be introduced into thepolymer, for example, using correspondingly functionalized monomerscontaining amino groups which are incorporated in the monomers formingR¹¹ in a copolymerization reaction. However, the polymers may also beprovided with functional groups Z after polymerization in a suitablepolymer-analog reaction. Corresponding reactions are known to theexpert.

Monomers suitable for introducing amino groups into the polymers are,for example, 2-aminoethyl acrylamide, 2-aminoethyl methacrylamide,3-aminopropylacrylamide, 3-aminopropyl methacrylamide and allylamine.

The polymers containing amino groups as functional groups Z may then beconverted in a polymer-analog reaction into compounds corresponding togeneral formula VI which contain a carbamate group as the functionalgroup Z. A corresponding polymer-analog reaction, for example withorganic carbonates, may be carried out by the scheme already describedin the foregoing.

If the corresponding polymer contains more than one amino group, theconversion of amino groups into carbamate groups may be carried outcompletely or only partly.

In addition, polyesters may be used as the polymers R¹¹ in accordancewith the invention. Suitable polyesters may be obtained in known mannerby polycondensation of acid and alcohol components, more particularly bypolycondensation of a polycarboxylic acid or a mixture of two or morepolycarboxylic acids and a polyol or a mixture of two or more polyols.

Polycarboxylic acids suitable in accordance with the present inventionfor the production of the polyester usable as R¹¹ may be based on analiphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic parentcompound and, besides the at least two carboxylic acid groups, mayoptionally contain one or more substituents which do not react in apolycondensation reaction, for example halogen atoms or olefinicallyunsaturated double bonds. The free carboxylic acids may even be replacedby their anhydrides (where they exist) or esters with C₁₋₅ monoalcoholsor mixtures of two or more thereof for the polycondensation reaction.

Suitable polycarboxylic acids are, for example, succinic acid, adipicacid, suberic acid, azelaic acid, sebacic acid, glutaric acid, glutaricanhydride, phthalic acid, isophthalic acid, terephthalic acid,trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride,hexahydrophthalic anhydride, tetrachlorophthalic anhydride,endomethylene tetrahydrophthalic anhydride, glutaric anhydride, maleicacid, maleic anhydride, fumaric acid, dimer fatty acids or trimer fattyacids or mixtures of two or more of the polycarboxylic acids mentioned.Small quantities of monofunctional fatty acids may optionally be presentin the reaction mixture.

Various polyols may be used as the diols for producing a polyester orpolycarbonate usable as R¹¹ in a compound corresponding to generalformula VI. Examples of such polyols are aliphatic polyols containing 2to 4 OH groups per molecule. These OH groups may be both primary andsecondary OH groups. Suitable aliphatic polyols include, for example,ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol,butane-1,3-diol, butane-2,3-diol, butene-1,4-diol, butine-1,4-diol,pentane-1,5-diol, and the isomeric pentanediols, pentenediols orpentinediols or mixtures of two or more thereof, hexane-1,6-diol and theisomeric hexanediols, hexenediols or hexinediols or mixtures of two ormore thereof, heptane-1,7-diol and the isomeric heptane, heptene orheptinediols, octane-1,8-diol and the isomeric octane, octene oroctinediols and higher homologs or isomers of the compounds mentioned,which are obtained in known manner from a step-by-step extension of thehydrocarbon chain by one CH₂ group at a time or by introducing branchesinto the carbon chain, or mixtures of two or more thereof.

Other suitable polyols are alcohols of relatively high functionality,such as glycerol, trimethylol propane, pentaerythritol or sugaralcohols, such as sorbitol or glucose, and oligomeric ethers of thesubstances mentioned either as such or in the form of a mixture of twoor more of the compounds mentioned with one another, for examplepolyglycerol with a degree of polymerization of about 2 to about 4. Inthe alcohols of relatively high functionality, one or more OH groups maybe esterified with monobasic carboxylic acids containing 1 to about 20carbon atoms, with the proviso that, on average, at least two OH groupsremain intact. The alcohols mentioned with a functionality of more than2 may be used in pure form or, where possible, in the form of thetechnical mixtures obtainable in the course of their synthesis.

The reaction products of low molecular weight polyfunctional alcoholswith alkylene oxides, so-called polyether polyols, may also be used aspolyol component for the production of the polyesters. Polyetherpolyols, which are to be used for the production of polyesters suitableas R¹¹, are preferably obtained by reaction of polyols with alkyleneoxides. The alkylene oxides preferably contain 2 to about 4 carbonatoms. Suitable polyether polyols are, for example, the reactionproducts of ethylene glycol, propylene glycol, the isomeric butanediolsor hexanediols, as mentioned above, or mixtures of two or more thereofwith ethylene oxide, propylene oxide or butylene oxide or mixtures oftwo or more thereof. Other suitable polyether polyols are products ofthe reaction of polyhydric alcohols, such as glycerol, trimethylolethane or trimethylol propane, pentaerythritol or sugar alcohols ormixtures of two or more thereof with the alkylene oxide mentioned toform polyether polyols. Polyether polyols with a molecular weight(M_(n)) of about 100 to about 3,000 and preferably in the range fromabout 200 to about 2,000 obtainable from the reactions mentioned areparticularly suitable. The polyether polyols mentioned may be reactedwith the polycarboxylic acids mentioned above in a polycondensationreaction to form the polyesters suitable for use as the polymers R¹¹.

The functionalization of the polymers R¹¹ with corresponding functionalgroups Z may be carried out in known manner. Polyesters containing acarboxylic acid group as terminal group are particularly suitable forfunctionalization. Polyesters such as these may be reacted withpolyamines, for example, in a polymer-analog reaction so that thepolyester contains terminal amino groups. If the polyester is providedwith amino groups in a polymer-analog reaction, it would also bepossible, for example, to use polyesters containing terminal carboxylicacid groups or lateral and terminal amino groups which are subsequentlyfunctionalized with polyamines to form aminofunctional polyesters.

The polyesters containing amino groups as functional groups Z may thenbe converted in a polymer-analog reaction into compounds correspondingto general formula VI which contain a carbamate group as the functionalgroup Z. A corresponding polymer-analog reaction, for example withorganic carbonates, may be carried out to the scheme already describedin the foregoing.

Polyether polyols are also suitable for as the polymers R¹¹. Suitablepolyether polyols are normally obtained by reacting a starting compoundcontaining at least two reactive hydrogen atoms with alkylene or aryleneoxides, for example ethylene oxide, propylene oxide, butylene oxide,styrene oxide, tetrahydrofuran or epichlorohydrin or mixtures of two ormore thereof.

Suitable starting compounds are, for example, water, ethylene glycol,1,2- or 1,3-propylene glycol, 1,4- or 1,3-butylene glycol,1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-hydroxymethylcyclohexane, 2-methylpropane-1,3-diol, glycerol, trimethylol propane,hexane-1,2,6-triol, butane-1,2,4-triol, trimethylol ethane,pentaerythritol, mannitol, sorbitol, methyl glycosides, sugars, phenol,isononyl phenol, resorcinol, hydroquinone, 1,2,2- or1,1,2-tris-(hydroxyphenyl)-ethane, ammonia, methyl amine,ethylenediamine, tetra- or hexamethylenediamine, triethanolamine,aniline, phenylenediamine, 2,4- and 2,6-diaminotoluene and polyphenylpolymethylene polyamines which can be obtained by condensing anilinewith formaldehyde.

Polyether polyols modified by vinyl polymers are also suitable for useas the polymers R¹¹. Products such as these can be obtained, forexample, by polymerizing styrene or acrylonitrile or a mixture thereofin the presence of polyethers.

The polyether polyols are functionalized in known manner. For example,conventional polyether polyols may be converted into the correspondingpolyetheramines by reacting the terminal OH groups with ammonia orprimary amines using methods known from the literature.

Corresponding polyether polyols are commercially obtainable in variouscompositions, for example under the name of JEFFAMIN®. Examples includethe Jeffamin types D 230, D 400 and D 2000 based on difunctionalpolypropylene glycols, the types T 403, T 3000 and T 5000 based ontrifunctional polypropylene glycols, the types ED 600, ED 900, ED 2001and ED 6000 based on difunctional polyethylene glycols and the types M300, M 600, M 1000 and M 2070 based on monofunctional polypropyleneglycols.

Suitable aminofunctional polyethers may be converted by polymer-analogfunctionalization into polymers which contain a carbamate group as thefunctional group Z.

Polyacetals are also suitable for use as the polymers R¹¹. Polyacetalsare understood to be compounds obtainable by reacting glycols, forexample diethylene glycol or hexanediol, with formaldehyde. Polyacetalssuitable for the purposes of the invention may also be obtained bypolymerizing cyclic acetals. The foregoing observations in thedescription of the polyesters apply to the functionalization of thepolyacetals with functional groups Z.

Polycarbonates are also suitable for use as the polymers R¹¹.Polycarbonates may be obtained, for example, by reacting the polyolsmentioned above, more particularly diols, such as propylene glycol,butane-1,4-diol or hexane-1,6-diol, diethylene glycol, triethyleneglycol or tetraethylene glycol or mixtures of two or more thereof, withdiaryl carbonates, for example diphenyl carbonate or phosgene. Theforegoing observations in the description of the polyesters apply to thefunctionalization of the polycarbonates with functional groups Z.

Polylactones are also suitable for use as the polymers R¹¹. Preferredpolylactones are derived from compounds with the general formulaHO—(CH₂)_(z)—COOH, where z is a number of 1 to about 20. Examples areε-caprolactone, β-propiolactone, γ-butyrolactone ormethyl-ε-caprolactone or mixtures of two or more thereof. The foregoingobservations in the description of the polyesters apply to thefunctionalization of the polylactones with functional groups Z.

Polyethyleneimines are also suitable for use as the polymers R¹¹.Suitable polyethyleneimines can be obtained by polymerizing reaction ofethyleneimine and have a molecular weight of about 300 to about 100,000.

Polyamides are also suitable for use as the polymers R¹¹ in accordancewith the invention. Suitable polyamides can be obtained, for example, byreaction of the above-mentioned dicarboxylic acids with correspondingdiamines. Suitable diamines are, for example, those which have amolecular weight of about 32 to about 200 g/mol and which contain atleast two primary, two secondary or one primary and one secondary aminogroup. Examples of such diamines are diaminoethane, diaminopropanes,diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine,amino-3-aminomethyl-3,5,5-trimethyl cyclohexane (isophorone diamine,IPDA), 4,4′-diaminodicyclohexylmethane, 1,4-diaminocyclohexane,aminoethyl ethanolamine, hydrazine, hydrazine hydrate or—optionally insmall quantities—diamines, such as diethylenetriamine or1,8-diamino-4-aminomethyl octane. Synthesis from lactams, such asε-caprolactam, or aminocarboxylic acids, such as 11-aminoundecanoicacid, is also possible.

The molecular weights of the compounds of general formula VI usable inthe process according to the invention is preferably in the range fromabout 300 to about 1,000,000. If a polymer is to be used as the compoundof general formula VI, a polymer with a molecular weight of about 500 toabout 300,000 and more particularly in the range from about 1,000 toabout 30,000 is preferably used.

If a polyester to used as the compound corresponding to general formulaVI, it preferably has a molecular weight of about 300 to about 100,000,for example in the range from about 500 to about 50,000 or in the rangefrom about 1,000 to about 30,000.

If a polyether to used as the compound corresponding to general formulaVI, it preferably has a molecular weight of about 300 to about 100,000,for example in the range from about 500 to about 50,000 or in the rangefrom about 1,000 to about 30,000, for example in the range from about3,000 to about 20,000 or in the range from about 4,000 to about 8,000 orabout 12,000.

Suitable molecular weights for polycarbonates, polylactones,polyethyleneimines or polyamides usable as polymers corresponding togeneral formula VI in accordance with the invention are preferably inthe range from about 300 to about 50,000 and more particularly in therange from about 1,000 to about 30,000.

In another embodiment of the present invention, the compoundscorresponding to general formula VI may contain one or more silyl groupscorresponding to general formula II besides the functional groups Z asfunctional groups.

According to the invention, the process according to the invention iscarried out by reacting a compound containing at least one amino groupwith a carbamate, at least one of the reactants carrying a silyl group.Accordingly, another possible embodiment of the present invention ischaracterized, for example, by the reaction of two compoundscorresponding to general formula III, of which one compound carries anamino group and the other a carbamate group, with one another. Inanother embodiment of the invention for example, one compoundcorresponding to general formula III is reacted with one compoundcorresponding to general formula VI or two compounds corresponding togeneral formula VI are reacted with one another, with the proviso thatone of the reactants bears an amino group and the other reactant acarbamate group. Besides reacting two of the compounds mentioned, it isalso possible in accordance with the invention to react three or moredifferent compounds corresponding to general formula III or to generalformula VI or mixtures of two or more different compounds correspondingto general formula III with one or more compounds corresponding togeneral formula VI or mixtures of two or more compounds corresponding togeneral formula VI with a compound corresponding to general formula III.

In a preferred embodiment of the invention, the reaction on which theprocess according to the invention is based takes place in the presenceof a catalyst. Suitable catalysts are, for example, compoundscorresponding to general formula VII:M(OR¹²)_(x)  (VII)in which M is a metal selected from the group consisting of aluminium,titanium, magnesium or zirconium and R¹² stands for the same ordifferent, linear or branched hydrocarbon radicals containing 1 to 8carbon atoms and x has a value of 2, 3 or 4. Suitable catalysts are, forexample, aluminium alkoxides, titanium alkoxides, magnesium alkoxidesand zirconium alkoxides. Particularly suitable catalysts are, forexample, aluminium trimethoxide, aluminium triethoxide, aluminiumtriisopropoxide, aluminium trisec.butoxide, aluminium tritert.butoxide,titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV)isopropoxide, titanium(IV) butoxide, titanium(IV) 2-ethylhexoxide,zirconium(IV) ethoxide, zirconium(IV) propoxide, zirconium(IV) butoxide,zirconium(IV) isopropoxide, zirconium(IV) tert.butoxide, magnesiummethoxide, magnesium ethoxide, magnesium butoxide, magnesium propoxideor magnesium phenoxide.

Other suitable catalysts for the process according to the invention aretin compounds, more particularly organotin carboxylates, such asdibutyltin dilaurate, dibutyltin diacetate, dibutyltinbis-(2-ethylhexanoate) or other organotin compounds, such as dibutyltinoxide, dibutyltin dimethoxide, dibutyltin dibromide, dibutyltindichloride, ditert.butyltin dichloride, dimethyltin dibromide,dimethyltin dichloride, diphenyltin dichloride or tin octoate. Of thecatalysts mentioned, dibutyltin dilaurate, dibutyltin oxide anddibutyltin diacetate are preferred.

Other suitable catalysts are compounds which contain at least one metalselected from the group consisting of antimony, iron, cobalt, nickel,copper, chromium, maganese, molybdenum, tungsten or lead. The oxides,halides, carboxylates, phosphates or organometallic compounds of themetals mentioned are particularly suitable. Examples of particularlysuitable catalysts include iron acetate, iron benzoate, ironnaphthenates; iron acetyl acetonates, manganese acetate, manganesenaphthenate and manganese acetyl acetonate.

The quantity of catalyst used in the process according to the inventionis in the range from about 0.01 to about 0.5% by weight and moreparticularly in the range from about 0.05 to about 0.2% by weight.

The process according to the invention is preferably carried out at a pHof about 2 to about 12 and more particularly at a pH of about 5 to about9, for example at a pH of about 5.5 to about 8.5.

The process according to the invention may be carried out in the absenceof solvents or in an organic solvent. Suitable organic solvents have aboiling point of at least about 100° C. and preferably higher. Suitablesolvents are, for example, dioctyl phthalate, didecyl phthalate,didoceyl phthalate and other homologous esters of polybasic carboxylicacids. Other suitable organic solvents are phosphoric acid esters, forexample chlorinated phosphoric acid esters, and also dibenzyltoluene,triphenylmethane, phenylnaphthalene, biphenyl, diethylbiphenyl ortriethylbiphenyl. Basically, any solvents with a sufficiently highboiling point may be used providing they are inert to the reactants.

In a preferred embodiment of the invention, the solvent is a solventwhich is used in a subsequent formulation involving the compoundsaccording to the invention, for example as plasticizers, and which maytherefore remain in the prepolymer.

The reaction is preferably carried out at a temperature of about 50 toabout 300° C. and more particularly as a temperature of about 50 toabout 250° C. Suitable reaction temperatures are, in particular, in therange from about 80 to about 220° C. or up to about 190° C.

The reaction time is between about 0.1 and about 10 hours, depending onthe temperature and the catalyst(s) used. In a preferred embodiment ofthe invention, the reaction conditions are selected so that the reactiontime is between about 0.5 and about 1.5 hours. The progress of thereaction may be followed, for example, by monitoring the amine value inthe reaction mixture. The reaction is preferably continued until theamine value has fallen to a value of about 5 or less, for example to avalue of 1 or less, more particularly to a value of 0.5 or less.

On completion of the reaction, i.e. after the required amine value hasbeen reached, the reaction mixture is cooled. Depending on the requiredconduct of the reaction, the pressure may be reduced during cooling, forexample, so that any readily volatile constituents, such as lowmolecular weight alcohols or any solvent used, are removed in vacuo.

The above-mentioned reactants may be used in various molar ratios in theprocess according to the invention. Basically, any ratios of aminogroups to carbamate groups may be used. In a preferred embodiment,however, the ratio of amino groups to carbamate groups is selected sothat it is at most about 1:1. This ensures that substantially everyamino group reacts with a carbamate group.

Another embodiment of the present invention is characterized by aconduct of the reaction in which the reactant carrying the carbamategroups has at least two carbamate groups. In this case, anotherembodiment of the invention is characterized in that the ratio ofcarbamate groups to amino groups is 1 or less than 1, for example about0.1 to about 0.99 or about 0.3 to about 0.9 or about 0.4 to about 0.8.

Basically, suitable reactants containing at least two carbamate groupsare any reactants carrying at least two carbamate groups whichcorrespond to general formula VI. Suitable compounds may be produced,for example, from the above-described compounds carrying at least twoamino groups in the manner already described.

In a preferred embodiment of the present invention, however, a polymeris used as the reactant containing at least two carbamate groups.

Suitable polymers containing at least two carbamate groups can beproduced from the polymers containing at least two amino groups alreadydescribed in the foregoing in the manner already described.

In a preferred embodiment of the present invention, a polymer containingat least one ether group is used as the polymer containing at least twocarbamate groups. In another preferred embodiment of the presentinvention, a polyether or a polyamide or a polyurea or a mixture of twoor more thereof is used as the polymer containing at least two carbamategroups.

According to the invention, a compound containing an amino group or acompound containing two or more amino groups is used as reactant for thecompound containing at least two carbamate groups or the mixture of twoor more such compounds. In a preferred embodiment, however, a compoundcontaining only one amino group is used.

According to the invention, at least the reactant containing the aminogroup(s) preferably contains one or more silyl groups. In a preferredembodiment of the invention, a polymer containing at least two carbamategroups or a mixture of two or more such polymers and an aminosilane or amixture of two or more aminosilanes are used as reactants.

If the reaction according to the invention between a compound containingat least two carbamate groups or a mixture of two or more thereof and acompound containing one or more amino groups is carried out in such away that the ratio of amino groups to carbamate groups is <1, theprocess according to the invention is preferably carried out in thepresence of a trimerization catalyst. In the reaction on which theprocess according to the invention is based, isocyanurate groups areformed in the presence of a trimerization catalyst.

According to the invention, the reaction according to the invention(cracking/trimerization reaction) may be carried out, for example, untilthe reaction mixture no longer contains carbamate groups. In anotherembodiment of the present invention, however, the reaction isincomplete. In the context of the invention, an “incomplete reaction” isunderstood to be a reaction in which not all the carbamate groupspresent in the reaction mixture are reacted, i.e. in which carbamategroups remain in the reaction product. Basically, this variant of theprocess according to the invention is suitable for any combinations ofreactants where at least one reactant carries at least one carbamategroup. However, this variant is particularly advantageous when one ofthe reactants contains at least two carbamate groups.

Accordingly, the present invention also relates to a polymer whichcontains at least one urea group, at least one alkoxysilyl group and atleast one carbamate group. In another embodiment of the presentinvention, this polymer may additionally contain, for example, one ormore isocyanurate groups.

The reaction may readily be terminated by methods known to the expert,for example by the addition of a catalyst poison or by lowering thetemperature.

The effect of the remaining carbamate groups is that the reactionproduct has a lower viscosity than the fully reacted product and hencesimplifies use as a binder for adhesives and sealants. In addition, theremaining carbamate groups may additionally be used for formulatingheat-activatable adhesives and sealants because the carbamate groupssplit at temperatures above 150° C. to give the isocyanate and can befurther crosslinked by trimerization or allophanatization.

Trimerization catalysts are known to the expert from the relevantliterature (see, for example, Laas et al., J. prakt. Chem. 336 (1994),pages 192 to 196 and various patent publications, such as U.S. Pat. No.5,218,133 (Union Carbide), U.S. Pat. No. 4,412,073 (Rhone-Poulenc), U.S.Pat. No. 5,260,436 (Iowa), U.S. Pat. No. 5,837,796 (Bayer) and U.S. Pat.No. 4,124,545 (Bayer)). Suitable trimerization catalysts are, forexample, the catalysts already described in the foregoing in connectionwith the reaction of carbamate groups and amino groups. Other suitabletrimerization catalysts are the alkali metal salts of organic acids oralkali metal salts of phosphoric acid and also amines which do not reactwith the carbamate groups. Examples of alkali metal salts of organicacids include the sodium, potassium, lithium or caesium salts of aceticacid, propionic acid, butyric acid, hexanoic acid, oleic acid, maleicacid, fumaric acid, succinic acid and the like. Examples of alkali metalsalts of phosphoric acid include, for example, alkali metalorthophosphates, such as trisodium orthophosphate, tripotassiumorthophosphate or dipotassium orthophosphates, such as disodiumorthophosphate or dipotassium orthophosphate. Amines suitable astrimerization catalysts are, for example, tertiary amines, such asN,N-dimethyl dodecylamine, 1,4-diazabicyclo-[2.2.2]-octane (DABCO).Mixtures of two or more of the compounds mentioned are also suitable.

In a preferred embodiment of the present invention, either an organotincompound, more particularly dibutyltin dilaurate, aluminiumtriisopropylate, iron(II) acetyl acetonate or a mixture of the catalystsmentioned is used as the trimerization catalyst. Catalysts whichsimultaneously catalyze cracking and trimerization, for examplealuminium triisopropylate, are particularly preferred.

It is possible by the process according to the invention to producepolymers which, in contrast to polymers containing isocyanuratestructures, contain only one isocyanurate group and three urea groupsand three silyl groups or, if the ratio of carbamate groups to aminogroups is selected accordingly, several triisocyanurate groups and acorresponding number of urea groups and silyl groups. However, in thecase of those polymers which contain more than one isocyanurate group,no other structural element obtainable by reaction of isocyanate groupswith an isocyanate-reactive compound is present between two isocyanurategroups.

Accordingly, the present invention also relates to a polymer whichcontains at least one isocyanurate structural element and at least onealkoxysilyl group. If the polymer contains more than one isocyanuratestructural element, no structural element which can be formed byreaction of an isocyanate group with an isocyanate-reactive functionalgroup is present between at least two isocyanurate structural elementsin the polymer or the structure lying between two isocyanurate groupshas a molecular weight of at least 300.

In the context of the present invention, a “structure lying between twoisocyanurate groups” is understood to be a chain of covalently bondedatoms. The polymers according to the invention contain either only oneisocyanurate structural element, at least one urea group and at leastone alkoxysilyl group or more than one isocyanurate structural element,at least one urea group and at least one alkoxysilyl group. If a polymeraccording to the invention contains more than one isocyanuratestructural element, it has to satisfy various requirements. Either nostructural element obtainable by reaction of an isocyanate group with anisocyanate-reactive functional group is present between at least twoisocyanaurate structural elements in the polymer, i.e. no urethanegroup, urea group or oxazolidone group is present between at least twoisocyanurate groups.

Corresponding polymers according to the invention can be obtained, forexample, when compounds containing at least two carbamate groups whichhave no structural elements obtainable by the reaction of an isocyanategroup with an isocyanate-reactive compound in the substituent R¹¹ areused as the compounds corresponding to general formula VI. Substantiallyall the polymers already mentioned in the foregoing are suitable.

The term “molecular weight” as used in the present specification appliesto the molecular weight determined by GPC under conditions typical ofthe particular polymer, based on polystyrene as standard.

The polymers according to the invention may be produced by reaction of aprepolymer containing at least two carbamate groups or a mixture of twoor more such prepolymers with an alkoxysilane containing at least oneamino group, the molar ratio of carbamate group to amino groups beingless than 1.

Accordingly, the present invention also relates to a polymer obtainableby reaction of a prepolymer containing at least two carbamate groups ora mixture of two or more such prepolymers with an alkoxysilanecontaining at least one amino group, the molar ratio of carbamate groupsto amino groups being less than 1.

A “prepolymer” in the context of the invention is understood to be acompound corresponding to general formula VI which contains at least twofunctional groups Z, at least two of the functional groups Z being acarbamate group. A prepolymer according to the invention has a molecularweight of at least about 150 and at most about 1,000,000 and preferablyin the range from at least about 500 to about 50,000, for example in therange from about 1,000 to 50,000.

The compounds produced by the process according to the invention and thepolymers according to the invention are suitable, for example, for usein surface coating compositions, such as paints or similar coatingsystems, and for use in adhesives, sealants and foams.

Accordingly, the present invention also relates to the use of a compoundproduced by the process according to the invention or of a polymeraccording to the invention for the production of surface coatingcompositions, sealants, adhesives, for example pressure-sensitiveadhesives or hotmelt adhesives, assembly or insulating foams.

The present invention also relates to a surface coating composition oran adhesive at least containing a polymer produced by a processaccording to the invention or a polymer according to the invention.

In a preferred embodiment of the invention, surface coating compositionsor adhesives contain a crosslinking catalyst which catalyzes thecrosslinking of the silyl groups or a mixture of two or more suchcatalysts.

Suitable crosslinking catalysts are, for example, amino compounds, suchas triethylenediamine, trimethylaminoethyl piperazine, pentamethyldiethylenetriamine, tetramethyl iminoisopropylamine orbis-(dimethylaminopropyl)-N-isopropanolamine or dimorpholinodiethylether. Other suitable catalysts are those based on organic or inorganicheavy metal compounds, such as cobalt naphthenate, dibutyl tindilaurate, tin mercaptides, tin dichloride, zirconium tetraoctoate,antimony dioctoate, lead dioctoate, metal—more particularly iron—acetylacetonate. Any of the known catalysts for accelerating the condensationof silanols are particularly suitable. Examples of such catalystsinclude organotin, organotitanium, organozirconium- or organoaluminiumcompounds. Examples of such compounds are dibutyltin dilaurate,dibutyltin dimaleate, tin octoate, isopropyl triisostearoyl titanate,isopropyltris-(dioctylpyrophosphate)-titanate,bis-(dioctylpyrophosphate)-oxyacetate titanate, tetrabutyl zirconate,tetrakis-(acetylacetonato)-zirconium, tetraisobutyl zirconate,butoxytris-(acetylacetonato)-zirconium,tris-(ethylacetoacetato)-aluminium. Dibutyltin alkylesters, such asdibutyltin alkylmaleates or dialkyltin laurates, are particularlysuitable, more particularly dibutyltin bis-ethylmaleate, dibutyltinbis-butylmaleate, dibutyltin bis-octylmaleate, dibutyltinbis-oleylmaleate, dibutyltin bis-acetylacetate, dibutyltin diacetate,dibutyltin dioctoate, dibutyltin oxide, dibutyltin bistriethoxy silicateand catalytically active derivatives thereof. The catalysts mentionedmay be used individually or in the form of a mixture of two or more.

A crosslinking catalyst may be used, for example, in a quantity of 0.01%to about 2% and preferably in a quantity of 0.05% to about 0.5%, basedon the weight of the silyl groups.

In another embodiment of the present invention, a surface coatingcomposition according to the invention or an adhesive according to theinvention may contain further additives. Suitable additives are, forexample, tackifiers, plasticizers, rheological additives, antioxidants,UV stabilizers, dyes, pigments, adhesion promoters, drying agents, flameretardants, cell regulators, propellent gases or fillers.

The storage stability of the compounds according to the invention or thecompositions produced from them can be increased, for example, byreactive silanes. Suitable reactive silanes are, for example,tetramethoxysilane, trimethoxy methyl silane or trimethoxy vinyl silanewhich are suitable for trapping water. The content of such compoundsshould not exceed 3% by weight, based on the mixture as a wholecontaining the reactive silane or the mixture of two or more reactivesilanes.

Suitable flame retardants are, for example, any of the usualphosphorus-containing compounds, more particularly elemental phosphorus,phosphates or phosphonates, for example triethyl phosphate ortrichloropropyl phosphate. Compounds such as these can have bothplasticizing and viscosity-adjusting properties. Other suitable flameretardants are, for example, diphenylcresyl phosphates, triphenylphosphate, dimethylmethane phosphonate and the like. In addition,chloroparaffins may also be used as flame retardants. Also suitable arehalogenated polyester or polyether polyols, for example commerciallyavailable brominated polyether poylol. Halogenated polyester orpolyether polyols may be incorporated, for example, in the polymersaccording to the invention.

If the compounds according to the invention, particularly the polymersaccording to the invention, are present in compositions suitable for theproduction of foams, these compositions may contain, for example, cellregulators or propellents or both. The cell regulators used are normallysilicone-based compounds. In a preferred embodiment of the presentinvention, liquid, crosslinkable polybutadiene, silicone oils orparaffin oils are used as the cell regulator. In a preferred embodimentof the invention, commercially available silicone stabilizers are usedas the stabilizers.

If the compounds according to the invention are to be used for theproduction of foams, they are preferably supplied to the user inpressurized containers (aerosol cans). A composition containing acompound according to the invention additionally contains at least onepropellent for dispensing the binders or binder compositions accordingto the invention from the aerosol cans. Suitable propellents are, forexample, low-boiling fluorocarbons, hydrocarbons or ethers or mixturesof two or more thereof. The fluorocarbons R124, R125, R134a, R142b, R143and R152a, R227, the pure hydrocarbons propane, butane and isobutane anddimethyl ether either individually or in the form of mixture of two ormore thereof are particularly preferred. In addition, CO₂, N₂O or N₂ maybe present as propellents. Any combinations of these gases are possible.For aerosol can formulations, propellent gas contents of 5 to 40% byweight and more particularly 5 to 20% by weight, based on thecomposition as a whole, are preferred. The content of gasesnon-condensible under the prevailing pressure conditions should begauged so that the volume based on the empty space of the pressurizedcontainer gives a pressure of about 8 to 10 bar, depending on therelevant national regulations for aerosol cans and pressurizedcontainers (where such regulations exist). Since no CO₂ is given offduring the crosslinking of the compounds according to the invention,sufficient propellent gas must be present both for dispensing and forfoaming.

The tackifiers used are, for example, hydrocarbon resins, moreparticularly C5 or C9 resins or C5-resin-modified C9 resins. Othersuitable tackifiers are resins based on pure hydrocarbon monomers, forexample resins obtainable from the polymerization of mixtures ofstyrene, α-methyl styrene and vinyl toluene. The hydrocarbon resinsmentioned may be partly hydrogenated or fully hydrogenated.

Also suitable for use as tackifiers are natural resins, such as gumrosin obtainable, for example, from trees and liquid rosin which isobtained, for example, in papermaking. The natural resins may be used inthe above-mentioned form as tackifiers although they may also be usedafter esterification with corresponding polyhydric alcohols aspentaerythritol esters, glycerol esters, diethylene glycol esters,triethylene glycol esters or methyl esters.

Polyterpene resins are also suitable tackifiers. Terpenes are obtainedin the separation of oleoresin acids from their natural solvents and canbe polymerized to polyterpene resins. Also suitable for use astackifiers are the terpene/phenol resins obtainable from polyterpeneresins by phenol modification.

In addition, the adhesive according to the invention may containstabilizers or antioxidants as additives. These generally include thephenols, the sterically hindered high molecular weight phenols,polyhydric phenols, sulfur- and phosphorus-containing phenols or amines.Suitable stabilizers are, for example, hydroquinone, hydroquinonemethylether, 2,3-(ditert.butyl)-hydroquinone,1,3,5-trimethyl-2,4,6-tris(3,5-ditert.butyl-4-hydroxybenzyl)-benzene;pentaerythritoltetrakis-3-(3,5-ditert-butyl-4-hydroxyphenyl)-propionate;n-octadecyl-3,5-ditert-butyl-4-hydroxyphenyl)-propionate;4,4-methylene-bis-(2,6-ditert.butylphenol);4,4-thiobis-(6-tert.butyl-o-cresol); 2,6-ditert.butylphenol;6-(4-hydroxyphenoxy)-2,4-bis-(n-octylthio)-1,3,5-triazine;di-n-octadecyl-3,5-ditert.butyl-4-hydroxybenzyl phosphonates;2-(n-octylthio)-ethyl-3,5-ditert.butyl-4-hydroxybenzoate; and sorbitolhexa-[3-(3,5-ditert.butyl-4-hydroxyphenyl)-propionate]; andp-hydroxydiphenylamine or N,N′-diphenylenediamine or phenothiazine.

The surface coating composition according to the invention or theadhesive according to the invention may additionally containplasticizers, such as benzoate plasticizers, phosphate plasticizers,liquid resin derivatives or vegetable and animal oils. Suitableplasticizers are, for example, sucrose benzoate, diethylene glycoldibenzoate and/or diethylene glycol benzoate where about 50 to about 95%of all hydroxyl groups have been esterified, phosphate plasticizers, forexample t-butylphenyl diphenyl phosphate, polyethylene glycols andderivatives thereof, for example diphenyl ethers of poly(ethyleneglycol), liquid resin derivatives, for example the methyl ester ofhydrogenated resin, vegetable and animal oils, for example glycerolesters of fatty acids and polymerization products thereof.

Plasticizers based on phthalic acid, particularly the alkyl phthalates,are also suitable.

The surface coating composition according to the invention or theadhesive according to the invention may additionally contain dyes, suchas titanium dioxide, fillers, such as gypsum, talcum, clay and the like,and pigments.

The additives may be present individually or in the form of a mixture oftwo or more of the substances mentioned. The quantity in which theadditives are present should not exceed about 20% by weight (based onthe surface coating composition as a whole or the adhesive as a whole).Suitable quantities are, for example, about 0.1 to about 15% by weightor about 1 to about 10% by weight, In a preferred embodiment of theinvention, the additives are used in quantities of, for example, about2, 3, 4, 5, 7 or 9% by weight.

Suitable surface coating compositions or adhesives have, for example,the following approximate composition:

Basic formulations:

Foams:

-   -   40–80% by weight prepolymer    -   10–25% by weight plasticizer or flame retardant    -   0–5% by weight foam stabilizer    -   0–2% by weight catalyst(s)    -   0–5% by weight other additives    -   10–25% by weight propellent gas        1. Sealant and Assembly Adhesive    -   25–50% by weight prepolymer    -   25–50% by weight filler(s)    -   0–25% by weight additives    -   >1% by weight catalyst(s)

The invention is illustrated by the following Examples.

EXAMPLES Example 1

51.7 g octylamine, 94.8 g methyl-N-(trimethoxysilylpropyl)-methylcarbamate and 0.1 g dibutyltin dilaurate were heated under nitrogen to180° C. After 3 h, the amine value had fallen from 153 to <10. Aftercooling to room temperature, a white solid was obtained.

Example 2 Silylation of Jeffamin T5000 withmethyl-N-(trimethoxysilylpropyl)-carbamate

385.0 g Jeffamin T5000 (propoxylated glycerol with terminal aminogroups, molecular weight ca. 5,000, amine value: 27.5) were weighed intoa 1-liter three-necked flask and dried at ca. 100° C. under a pressureof 20 mbar. After purging with nitrogen, 57.1 gN-(trimethoxysilylpropyl)-methylcarbamate and 0.1 g dibutyltin dilauratewere added and the whole was heated under nitrogen to 190° C. Within anhour, the amine value had fallen to 2.5. After cooling to roomtemperature, a clear liquid with a viscosity of ca. 100 Pas (BrookfieldRVT, spindle 6, 5 r.p.m.) was obtained.

0.2% dibutyl tin diacetonate was added to the liquid which was thenintroduced into a rectangular mold in a layer thickness of 2 mm andstored for 1 week at 50% relative humidity/23° C. for completehardening.

A colorless, flexible and elastic polymer film was obtained after fullcuring.

Comparison Example 1 Silylation of Jeffamin D4000 with3-isocyanatopropyl trimethoxysilane

106 g 3-isocyanatopropyl trimethoxysilane were added dropwise over aperiod of 20 mins. to 1,000 g Jeffamin D4000 (α,ω-aminopolypropyleneglycol, molecular weight ca. 4,000, amine value: 28); increase intemperature ca. 15° C. 1 hour after the end of the addition of theisocyanatosilane, no more isocyanate could be detected. A clearcolorless liquid with a viscosity of 5,000 mPas was obtained.

0.2% dibutyl tin dilaurate was added to the liquid which was thenintroduced into a rectangular mold in a layer thickness of 2 mm andstored for 1 week at 50% relative humidity/23° C. for completehardening.

24 hours after application, the surface of the cured film (catalyst 0.1%by weight dibutyltin bis-(2,4-pentanedionate)) was slightly tacky.

Example 3 Silylation of Jeffamin D4000 withmethyl-N-(trimethoxysilylpropyl)-carbamate

200.0 g Jeffamin D4000 were weighed into a 0.5 liter three-necked flaskand dried at ca. 100° C./20 mbar. After purging with nitrogen, 25.6 gN-(trimethoxysilylpropyl)-methylcarbamate and 0.1 g dibutyltin dilauratewere added and the whole was heated under nitrogen to 180° C. Within anhour, the amine value had fallen to 0.5. After cooling to <150° C., themixture was slowly cooled in vacuo (ca. 20 mbar) to room temperature. Aclear yellow liquid with a viscosity of 9,000 mPas (Brookfield RVT,spindle 6, 20 r.p.m.) was obtained.

24 hours after application, the cured film (catalyst 0.1% by weightdibutyltin-bis-(2,4-pentanedionate)) was flexible, elastic andtack-free.

Example 4 Silylation of a polyamide withmethyl-N-(trimethoxysilylpropyl)-carbamate

150.0 g Macromelt TPX 22-405 (polyamide with terminal amino groups) weremelted under nitrogen and 0.15 g dibutyltin dilaurate and 4.4 gN-(trimethoxysilylpropyl)-methylcarbamate were stirred into the melt.The mixture was then heated for ca. 2 h to 180–190° C. After cooling to<150° C., the mixture was slowly cooled in vacuo (ca. 20 mbar) to roomtemperature.

A transparent yellow solid was obtained.

Comparison Example 2 Silylation of a polyamide of dimer fatty acid andethyl nediamine with 3-isocyanatopropyl trimethoxysilane

24.5 g 3-isocyanatopropyl trimethoxysilane were added dropwise withstirring to 100 g of the polyamide at 80° C. (temperature increase ca.20° C.). One hour after the end of the addition of the isocyanatosilane,no more isocyanate could be detected. A yellow-brown, slightly cloudywax-like substance which melted at 70±5° C. was obtained. The cured,clear yellow film (catalyst 0.15% by weightdibutyltin-bis-(2,4-pentanedionate)) is hard and inelastic.

Example 5 Silylation of a polyamide of dimer fatty acid andethylenediamine with methyl-N-(trimethoxysilylpropyl)-carbamate

21.0 g methyl-N-(trimethoxysilylpropyl)-carbamate and 0.15 g dibutyltindilaurate were stirred into 100 g of the polyamide at 100° C. and theresulting mixture was stirred for 1 h at 180° C. It was then slowlycooled in vacuo (ca. 20 mbar) to room temperature. A yellow-brown,slightly cloudy wax-like substance which melted at 70±5° C. wasobtained. The cured, clear yellow film (catalyst 0.15% by weightdibutyltin-bis-(2,4-pentanedionate)) had the same properties as inComparison Example 2.

Example 6 Reaction of Jeffamin D 2000 to polyoxypropylene dicarbamateand subsequent pyrolysis in the presence of 3-aminopropyltrimethoxysilane

2 g of a 30% methanolic sodium methylate solution were stirred dropwiseinto 100 g water-free dimethyl carbonate, after which 250 g Jeffamin D2000 were added dropwise with stirring over a period of 30 minutes. Thereaction to the carbamate took place over a period of 5 hours at 75° C.and produced a yield of >90%. The sodium methylate was then neutralizedwith 0.6 g acetic acid, the salt was filtered off and the solventdistilled off.

The purified dicarbamate was then mixed with 44.8 g 3-aminopropyltrimethoxysilane and 0.3 g dibutyltin dilaurate and the resultingmixture was reacted at 180–190° C. as in Example 3 to form a silylatedprepolymer.

Example 7 Pyrolysis of 1,6-(di-N-methylcarbamato)-hexane in the presenceof bis-(trimethoxysilylpropyl)-amine

100 g 1,6-(di-N-methylcarbamato)-hexane, 73.2 gbis-(trimethoxysilylpropyl)-amine and 0.17 g dibutyltin dilaurate wereweighed into a 0.25 liter three-necked flask and the mixture was heatedwith vigorous stirring under nitrogen to 190° C. After 30 mins., avacuum (300 mbar) was applied. After another 30 mins., the vacuum wasreduced to about 20 mbar and the mixture was slowly cooled to roomtemperature.

A yellow-brown, soft resin was obtained.

1. A process for the production of compounds containing at least oneisocyanurate group, at least one urea group and at least one silyl groupcomprising reacting a compound containing at least one amino group and acarbamate compound together as reactants, wherein at least one of thereactants carries a silyl group.
 2. The process of claim 1 wherein thereaction is carried out in the presence of a catalyst.
 3. The process ofclaim 1 wherein the reactants further comprise at least one of methylcarbamate or ethyl carbamate.
 4. The process of claim 2 wherein thecatalyst is selected from the group consisting of organic bases andorganometallic compounds.
 5. The process of claim 1 wherein at least onepolymer is used as the at least one reactant.
 6. The process of claim 5wherein the polymer is selected from the group consisting ofpolyacrylates, polymethacrylates, polystyrenes, polyesters, polyethers,polyamides, polyurethanes, polycarbonates, polylactones, polyethyleneimine, polyureas, polyolefins and polyoxazolidones.
 7. The process ofclaim 1 wherein the at least one reactant contains at least twocarbamate groups.
 8. The process of claim 7 wherein the reactantcontaining at least two carbamate groups is a polymer.
 9. The process ofclaim 7 wherein the reaction is carried out in the presence of atrimerization catalyst.
 10. The process of claim 1 wherein not all ofthe carbamate groups are reacted.
 11. The process of claim 1 wherein atleast one compound containing a silyl group, a urea group and acarbamate group is present after the reaction.
 12. A method for theproduction of surface coating compositions, sealants, adhesives orassembly or insulating foams comprising addition of a compound producedby the method of claim 1 to a surface coating composition, a sealant,and adhesive or assembly, or an insulating foam.